CN103804678A - Fatty acid polyoxyethylene succinate and preparation method thereof and micro cutting solution prepared from fatty acid polyoxyethylene succinate - Google Patents
Fatty acid polyoxyethylene succinate and preparation method thereof and micro cutting solution prepared from fatty acid polyoxyethylene succinate Download PDFInfo
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- CN103804678A CN103804678A CN201410045982.6A CN201410045982A CN103804678A CN 103804678 A CN103804678 A CN 103804678A CN 201410045982 A CN201410045982 A CN 201410045982A CN 103804678 A CN103804678 A CN 103804678A
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- acid
- succinate
- aliphatic acid
- acid polyethenoxy
- ether
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- -1 polyoxyethylene succinate Polymers 0.000 title claims abstract description 38
- 238000005520 cutting process Methods 0.000 title claims abstract description 14
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 8
- 239000000194 fatty acid Substances 0.000 title claims abstract description 8
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 13
- 150000004665 fatty acids Chemical class 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- 125000001931 aliphatic group Chemical group 0.000 claims description 39
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 12
- 150000002632 lipids Chemical class 0.000 claims description 11
- 239000013530 defoamer Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007866 anti-wear additive Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- LDPIQRWHBLWKPR-UHFFFAOYSA-N aminoboronic acid Chemical class NB(O)O LDPIQRWHBLWKPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010730 cutting oil Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013556 antirust agent Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 60
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 10
- 239000005642 Oleic acid Substances 0.000 description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 10
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 4
- 239000002173 cutting fluid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QQVGEJLUEOSDBB-KTKRTIGZSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CO)(CO)CO QQVGEJLUEOSDBB-KTKRTIGZSA-N 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 210000001138 tear Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
The invention provides a fatty acid polyoxyethylene succinate. The fatty acid polyoxyethylene succinate is is characterized by having a structure as shown in the specification, wherein n is an integer between 2-15; R is an alkyl with 7-19 carbon atoms. The fatty acid polyoxyethylene succinate has good lubricity, is dissolvable in water to be prepared a water soluble cutting solution, has excellent cooling performance and good biodegradability, simultaneously is a good surfactant, and can be used in other lubricants using oil as the main component to prepare an emulsion liquid.
Description
Technical field
The present invention relates to synthesising chemical technology field, specifically aliphatic acid polyethenoxy succinate and preparation method thereof and prepare micro cutting liquid with this ester.
Background technology
The lubricant usage quantitys such as the machining oil of conventional metals processing and lubrication and cooling use, refrigerant, emulsion are large, and traditional machining oil is all that employing mineral oil is base oil, in physical environment, be difficult for decomposing, additive used is mostly harmful to human body and environment, not only waste resource, also can cause the huge pollution of processing site and environment.In recent years the research of micro cutting technology is obtained to very large progress, reduced the harm that the discharge of a large amount of cutting fluid causes environment, but the workpiece processing to clean and just can enter next procedure toward contact, need to use a large amount of clean-out systems.
As the publication number Chinese patent that is CN101376863, disclose a kind of micro quantity lubrication system aluminum alloy cutting fluid and its production and use, adopted weight percent raw material to be prepared from: base oil 30%, sulfide isobutene 5～20%, clorafin 5～20%, thiophosphatephosphorothioate 5～20%, potassium borate 5～20%, tensio-active agent 10%, rust-preventive agent 5%.Although this cutting fluid has good lubrication performance, but the workpiece processing will clean and just can enter next procedure toward contact, need to use a large amount of clean-out systems, can bring larger pressure to environment.
Summary of the invention
In view of above defect, the object of the invention is to overcome the deficiencies in the prior art, in the production that provides a kind of some surface active property aliphatic acid polyethenoxy succinate that workpiece clear water good, that process just can easily clean and be applied to lubricant, obtain a kind of water-soluble micro cutting liquid of lubrication and cooling excellent performance.The workpiece simultaneously processing only uses clear water just can clean up entering before next procedure, easy and simple to handle, environmental protection, low-carbon (LC).
For achieving the above object, the invention provides a kind of aliphatic acid polyethenoxy succinate, it is characterized in that thering is following structure:
Wherein, the integer that n is 2～15;
R is alkyl, is preferably carbonatoms and is alkane or the alkene of 7～19.
In addition, the present invention also provides the preparation method of above-mentioned aliphatic acid polyethenoxy succinate, it is characterized in that: generated after aliphatic acid polyethenoxy ether by lipid acid and oxyethane polymerization reaction take place, then react generation aliphatic acid polyethenoxy succinate with succsinic acid.
Above-mentioned concrete reaction equation is:
Wherein, the integer that n is 2～15;
R is alkyl, is preferably carbonatoms and is alkane or the alkene of 7～19.
In addition, the present invention also provides above-mentioned aliphatic acid polyethenoxy succinate preparation method's concrete technology step:
Step 1, lipid acid is dropped in polymeric kettle, add after initiator, stir.
In this step, the mol ratio of lipid acid and oxyethane is 1:2～15, and lipid acid is preferably alkane acid or the olefin acid of 7～19 from carbonatoms.
In this step, initiator is alkali lye, generally be selected from the aqueous solution of sodium hydroxide or potassium hydroxide, be preferably the alkali lye that mass concentration is the relative saturation of 20-30%, the net content of initiator (sodium hydroxide by 100% or potassium hydroxide) is generally 0.3～0.5% of carboxylic acid and oxyethane gross weight.
Step 2, the in the situation that of protection of inert gas, add oxyethane, simultaneously stir be warming up to 90～110 ℃, pressure is adjusted to 0.25～0.35MPa, polyreaction obtains aliphatic acid polyethenoxy ether for 2～5 hours.
Wherein, rare gas element generally selects nitrogen, argon gas etc. to can be used as the rare gas element of protection gas.
General step is for to passing into air in nitrogen conversion still in polymeric kettle, in the time that nitrogen in polymeric kettle keeps malleation, oxyethane advanced to polymeric kettle with nitrogen feed tank.
Reaction times is adjusted according to the chain length of lipid acid and extent of polymerization.
After reaction finishes, as excessive in the viscosity of product, can be by adopting polymer-extruded by polymeric kettle of nitrogen.Product now can be pure products, can be also mixture.
Step 3, succsinic acid is added after aforesaid reaction vessel, add catalyzer.
Wherein, the mol ratio of lipid acid and succsinic acid is 2～2.1:1, is preferably 2:1.
Catalyzer is dilute sulphuric acid or Zeo-karb.
In the time that catalyzer is dilute sulphuric acid, its mass concentration is in 5%, and the quality of its effective constituent (i.e. 98% the vitriol oil) is 0.3～0.5% of aliphatic acid polyethenoxy ether and succsinic acid gross weight; In the time that catalyzer is Zeo-karb, the quality of Zeo-karb is 1～2% of aliphatic acid polyethenoxy ether and succsinic acid gross weight.
Step 4, the in the situation that of protection of inert gas, stir be warming up to 180～220 ℃, react 3～5 hours.
The concrete reaction times is depending on the selection of raw material.
Step 5, through decompression dewater and remove catalyzer after obtain aliphatic acid polyethenoxy succinate.
Wherein, in the time that the catalyzer of selecting is dilute sulphuric acid, with in sodium hydroxide or potassium hydroxide solution and unnecessary acid; In the time that the catalyzer of selecting is Zeo-karb, direct filtration is removed.
Aliphatic acid polyethenoxy succinate of the present invention can be two replacement esters, can be also the mixture of monoesters and dibasic acid esters.Be generally take dibasic acid esters product as main monoesters and the mix products of dibasic acid esters.
In addition, aliphatic acid polyethenoxy succinate provided by the invention can be used as soluble oil, tensio-active agent: as uses such as emulsifying agent, washing composition, whipping agent, wetting agents.
Especially, when the polymerization degree of epoxy vinyl is when more than 6, product water-soluble good, can be used for improving the water-soluble of this product.
In addition, the present invention also provides a kind of use micro cutting liquid prepared by above-mentioned aliphatic acid polyethenoxy succinate, it is characterized in that, is mixed together by the component of following mass percent:
Wherein, water soluble anti-rust agent can be selected from one or more the mixture in boric acid, borate, petroleum sodium sulfonate, carboxylic acyloxy amine salt, boric acid amide salt;
Water-soluble extreme pressure anti-wear additives can be selected from one or more the mixture in borate, phosphoric acid salt, molybdate, water-soluble organic-molybdenum, boric acid amide salt;
The mixture of optional one or more in polyethers defoamer, dimethyl silicone oil, Siloxane-Oxyalkylene Copolymers, higher alcohols defoamer, polysiloxane defoamers, the fatty acid ester compounded thing of higher alcohols, polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene of defoamer.
In addition, the present invention also provides a kind of use emulsion cutting oil prepared by above-mentioned aliphatic acid polyethenoxy succinate female agent, it is characterized in that, is made up of the component of following mass percent:
Aliphatic acid polyethenoxy succinate 5～20;
Lubricant auxiliary agent 80～95;
Wherein, lubricant auxiliary agent can be selected from mineral oil, vegetables oil, synthetic oil, rust-preventive agent, extreme pressure anti-wear additives, sterilant, defoamer, tensio-active agent the mixture of one or more;
Rust-preventive agent can be sulfonate conventional in this area, carboxylic acid, phosphoric acid ester, acid amides, benzotriazole, sorbyl alcohol direactive glyceride, pentaerythritol monooleate etc.
Extreme pressure anti-wear additives can have higher fastness to wear for chlorine class conventional in this area, sulphur class, Phosphorus, organo-metallic salt, can prevent or reduce metallic surface weares and teares under moderate duty condition the single or extreme-pressure anti-wear constituent that mixes.
Sterilant, defoamer can be selected from reagent conventional in this area.
Tensio-active agent can be selected from one or more the mixture in negatively charged ion, positively charged ion, nonionic, amphoterics.
The female agent of a kind of emulsion cutting oil that above-mentioned substance mix and blend is obtained adds 5-20 water doubly and uses in the time of production and application.
effect and the effect of invention
Aliphatic acid polyethenoxy sulphosuccinates provided by the invention itself has good oilness, water soluble is prepared into water-soluble metalworking liquid, cooling performance is good, it is again good tensio-active agent simultaneously, can be used in other lubricants take oil as main component and prepare emulsion, simultaneously itself biological degradability is good.
Therefore, the workpiece processing with the said products, without with an organic solvent wait can affect the material of environmental safety, health of human body, just can easily clean with clear water.
In addition, use the micro cutting liquid of aliphatic acid polyethenoxy succinate manufacture provided by the invention compared with prior art, there is good oilness and biodegradable, seldom the micro cutting liquid of amount just can meet the high-end requirement of metal processing, reduce the harm to environment and workman, dropping to minimum to the pollution of environment.
In addition, the present invention, by the control to reaction times, temperature, consumption etc., makes product of the present invention take dibasic acid esters product as primary product; The present invention is also moderate water-soluble by make product have to the adjustment of its polymerization degree and hydrocarbyl group, splendid by obtaining lubricity after composite the components such as itself and lubricant auxiliary agent, possess again the multifunctional fatty acid polyoxyethylene succinate compound of good water-soluble.
Embodiment
Embodiment 1
Step 1,282.47kg (1000mol) oleic acid is dropped in polymeric kettle, add the potassium hydroxide of 3kg to stir, then in polymeric kettle, pass into air in nitrogen conversion still, in the time that nitrogen in polymeric kettle keeps malleation, with nitrogen feed tank by 440.52 (10000mol) oxyethane advance polymeric kettle, stir and be warming up to 100 ℃ simultaneously, pressure is adjusted to 0.3MPa, after polyreaction 3.5 hours, polymer-extruded with nitrogen by polymeric kettle, is oleic acid polyoxyethylene (10) ether.
Step 2: oleic acid polyoxyethylene (10) ether and 59.045kg(500mol that step 1 reaction is generated) succsinic acid adds in reactor, add the Zeo-karb of 11kg, be filled with nitrogen and change out air in reactor and react, temperature of reaction is: 200 ℃; Reaction times is: 4 hours; After reaction, moisture is discharged in decompression, and decationize exchange resin, is oleic acid polyoxyethylene (10) ether succinate.
Embodiment 2:
Step 1,144.20kg (1000mol) isocaprylic acid is dropped in polymeric kettle, add the sodium hydroxide of 2.4kg to stir, then in polymeric kettle, pass into air in nitrogen conversion still, in the time that nitrogen in polymeric kettle keeps malleation, with nitrogen feed tank by 660.78 (15000mol) oxyethane advance polymeric kettle, stir and be warming up to 90 ℃ simultaneously, pressure is adjusted to 0.35MPa, after polyreaction 5 hours, polymer-extruded with nitrogen by polymeric kettle, is isocaprylic acid polyoxyethylene (15) ether.
Step 2: isocaprylic acid polyoxyethylene (15) ether and 59.045kg(500mol that step 1 reaction is generated) succsinic acid adds in reactor, add the aqueous solution containing vitriol oil 3.5kg, be filled with nitrogen and change out air in reactor and react, temperature of reaction is: 180 ℃; Reaction times is: 5 hours; Decompression discharge section moisture after reaction, it is 7～8 o'clock that hydro-oxidation potassium neutralizes pH, is isocaprylic acid polyoxyethylene (15) ether succinate.
Embodiment 3:
Step 1,284.48kg (1000mol) stearic acid is dropped in polymeric kettle, add the potassium hydroxide of 1.2kg to stir, then in polymeric kettle, pass into air in nitrogen conversion still, in the time that nitrogen in polymeric kettle keeps malleation, with nitrogen feed tank by 88.1kg (2000mol) oxyethane advance polymeric kettle, stir and be warming up to 110 ℃ simultaneously, pressure is adjusted to 0.25MPa, after polyreaction 2 hours, polymer-extruded with nitrogen by polymeric kettle, is stearic acid polyoxyethylene (2) ether.
Step 2: stearic acid polyoxyethylene (2) ether and 59.045kg(500mol that step 1 reaction is generated) succsinic acid adds in reactor, add the Zeo-karb of 8.6kg, be filled with nitrogen and change out air in reactor and react, temperature of reaction is: 220 ℃; Reaction times is: 3 hours; After reaction, moisture is discharged in decompression, and decationize exchange resin, is stearic acid polyoxyethylene (2) ether succinate.
Embodiment 4:
Step 1,200.32kg (1000mol) lauric acid is dropped in polymeric kettle, add the potassium hydroxide of 2kg to stir, then in polymeric kettle, pass into air in nitrogen conversion still, in the time that nitrogen in polymeric kettle keeps malleation, with nitrogen feed tank by 264.31kg (6000mol) oxyethane advance polymeric kettle, stir and be warming up to 95 ℃ simultaneously, pressure is adjusted to 0.3MPa, after polyreaction 4 hours, polymer-extruded with nitrogen by polymeric kettle, is lauric acid polyoxyethylene (6) ether.
Step 2: lauric acid polyoxyethylene (6) ether and 59.045kg(500mol that step 1 reaction is generated) succsinic acid adds in reactor, add the Zeo-karb of 7.8kg, be filled with nitrogen and change out air in reactor and react, temperature of reaction is: 190 ℃; Reaction times is: 4.5 hours; After reaction, moisture is discharged in decompression, and decationize exchange resin, is lauric acid polyoxyethylene (6) ether succinate.
Embodiment 5:
Step 1,302.46kg (1000mol) sylvic acid is dropped in polymeric kettle, add the sodium hydroxide of 2.6kg to stir, then in polymeric kettle, pass into air in nitrogen conversion still, in the time that nitrogen in polymeric kettle keeps malleation, with nitrogen feed tank by 528.62 (12000mol) oxyethane advance polymeric kettle, stir and be warming up to 105 ℃ simultaneously, pressure is adjusted to 0.32MPa, after polyreaction 3.5 hours, polymer-extruded with nitrogen by polymeric kettle, is sylvic acid polyoxyethylene (12) ether.
Step 2: sylvic acid polyoxyethylene (12) ether and 59.045kg(500mol that step 1 reaction is generated) succsinic acid adds in reactor, add the Zeo-karb of 13kg, be filled with nitrogen and change out air in reactor and react, temperature of reaction is: 210 ℃; Reaction times is: 3.5 hours; After reaction, moisture is discharged in decompression, and decationize exchange resin, is sylvic acid polyoxyethylene (12) ether succinate.
the effect of embodiment and effect
One, performance test
The test of performance and quality is carried out in the preparation of oleic acid polyoxyethylene (10) succinate A, B, C, tetra-sections of cuttings of D that we generate above-mentioned reaction.
A: by 5g oleic acid polyoxyethylene (10) succinate, 3g potassium tetraborate, the Potassium tripolyphosphate of 3g, the dimethyl silicone oil defoamer of 0.01g, the water of 88.99kg, mix and blend is processed into a kind of micro cutting liquid A.
B: by 50g oleic acid polyoxyethylene (10) succinate, 2g petroleum sodium sulfonate, the polysiloxane defoamers of 0.05g, the water of 47.95g, mix and blend is processed into a kind of micro cutting liquid B.
C: by 30g oleic acid polyoxyethylene (10) succinate, 1g isocaprylic acid acid amides, 1g trolamine boric acid ester, the water of 68g, mix and blend is processed into a kind of micro cutting liquid C.
D: by 10g oleic acid polyoxyethylene (10) succinate, the 32# white oil of 75g, 5g petroleum sodium sulfonate, 5g Arlacel-80,3g trolamine, 2g sterilant MBM mix and blend is prepared after a kind of emulsion cutting oil, adds the water of 1000g to stir a kind of emulsion cutting fluid C of preparation.
The contrast and experiment of physical and chemical index check as shown in Table 1.
The contrast and experiment table of < table one > physical and chemical index check
| Test subject | A | B | C | D | Test method |
| Kinematic viscosity (40 ℃ of@) mm 2/s | -- | 20.33 | 7.32 | -- | GB/T265 |
| PH value | 7.5 | 7.6 | 8.3 | 9.2 | SH/T0578 |
| 0 grade, damp and hot experiment monolithic cast iron | 24 hours | 72 hours | 72 hours | 48 hours | GB/T2361 |
| Four ball milling spot diameter mm | 0.54 | 0.36 | 0.43 | 0.49 | GB/T12583 |
The aliphatic acid polyethenoxy succinate compound relating to due to embodiment 2～5 also has as experimental result close in embodiment 1, therefore, no longer does redundancy herein and describes.
Two, biodegradability test
1. experimental technique: GB/T21856-2008 chemical fast degradation carbon dioxide generating test.
2. experiment material:
Prepared by 2.1 fluid: embodiment 1: oleic acid polyoxyethylene (10) ether succinate.
2.2 inoculums: take from 0-10cm place, different local earth's surface soil, soil sample is through mixing, after removal of impurities, get supernatant liquor by deionized water soaking and stirring.
3. experimental result:
28 days biological degradation rates are as calculated: 67.65%.
Claims (10)
1. an aliphatic acid polyethenoxy succinate, is characterized in that, has following structure:
Wherein, the integer that n is 2～15;
R is that carbonatoms is the alkyl of 7～19.
2. the preparation method of a kind of aliphatic acid polyethenoxy succinate as claimed in claim 1, it is characterized in that: generated after aliphatic acid polyethenoxy ether by lipid acid and oxyethane polymerization reaction take place, then react generation aliphatic acid polyethenoxy succinate with succsinic acid.
3. the preparation method of a kind of aliphatic acid polyethenoxy succinate as claimed in claim 2, is characterized in that, concrete technology step is as follows:
Step 1, lipid acid is dropped in polymeric kettle, add after initiator, stir;
Step 2, the in the situation that of protection of inert gas, add oxyethane, simultaneously stir be warming up to 90～110 ℃, pressure is adjusted to 0.25～0.35MPa, polyreaction obtains aliphatic acid polyethenoxy ether for 2～5 hours;
Step 3, the aliphatic acid polyethenoxy ether that step 2 is obtained and succsinic acid add after reactor, add catalyzer;
Step 4, the in the situation that of protection of inert gas, stir be warming up to 180～220 ℃, react 3～5 hours;
Step 5, through decompression dewater and remove catalyzer after obtain aliphatic acid polyethenoxy succinate;
Wherein, the mol ratio of described lipid acid and oxyethane is 1:2～15;
The mol ratio of described lipid acid and succsinic acid is 2～2.1:1.
4. the preparation method of a kind of aliphatic acid polyethenoxy succinate as claimed in claim 3, is characterized in that: described initiator is the aqueous solution of sodium hydroxide or potassium hydroxide.
5. the preparation method of a kind of aliphatic acid polyethenoxy succinate as claimed in claim 3, is characterized in that: the net content of described initiator is 0.3～0.5% of lipid acid and oxyethane gross weight.
6. the preparation method of a kind of aliphatic acid polyethenoxy succinate as claimed in claim 3, is characterized in that: described catalyzer is dilute sulphuric acid or Zeo-karb.
7. the preparation method of a kind of aliphatic acid polyethenoxy succinate as claimed in claim 6, is characterized in that: in described dilute sulphuric acid, the quality of effective constituent is 0.3～0.5% of described aliphatic acid polyethenoxy ether and succsinic acid gross weight;
The quality of described Zeo-karb is 1～2% of described aliphatic acid polyethenoxy ether and succsinic acid gross weight.
8. a kind of aliphatic acid polyethenoxy succinate as described in as arbitrary in claim 1-7, is characterized in that: described aliphatic acid polyethenoxy succinate can be used as soluble oil or tensio-active agent.
9. a micro cutting liquid of preparing with the aliphatic acid polyethenoxy succinate as described in as arbitrary in claim 1-7, is characterized in that, is made up of the component of following mass percent:
Wherein, described water soluble anti-rust agent can be selected from one or more the mixture in boric acid, borate, petroleum sodium sulfonate, carboxylic acyloxy amine salt, boric acid amide salt;
Described water-soluble extreme pressure anti-wear additives can be selected from one or more the mixture in borate, phosphoric acid salt, molybdate, water-soluble organic-molybdenum, boric acid amide salt;
The mixture of optional one or more in polyethers defoamer, dimethyl silicone oil, Siloxane-Oxyalkylene Copolymers, higher alcohols defoamer, polysiloxane defoamers, the fatty acid ester compounded thing of higher alcohols, polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, polypropylene glycerol aether and polyoxypropylene of described defoamer.
10. the female agent of emulsion cutting oil of preparing with the aliphatic acid polyethenoxy succinate as described in as arbitrary in claim 1-7, is characterized in that, is made up of the component of following mass percent:
Aliphatic acid polyethenoxy succinate 5～20;
Lubricant auxiliary agent 80～95;
Wherein, described lubricant auxiliary agent can be selected from mineral oil, vegetables oil, synthetic oil, rust-preventive agent, extreme pressure anti-wear additives, sterilant, defoamer, tensio-active agent the mixture of one or more.
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